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Chlorine Residuals Measurement

Terry Engelhardt
Application Development Manager –
Drinking Water
Hach Company

Reaction with Water


• Forms hydrochloric (HCl) and hypochlorous
(HOCl) acids:
Cl2 + H2O HOCl + H+ + Cl-
• Reaction is reversible. Above pH 4, reaction is to
the right
• HOCl dissociates to the hydrogen ion and
hypochlorite ion (OCl-) varying with temperature
and pH
HOCl H+ + OCl-

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HOCl vs. OCl-

Free Available Chlorine

• Chlorine existing in water as hypochlorous acid


(HOCl) or the hypochlorite ion (OCl-) is defined
as free available chlorine

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Hypochlorite Salts
• Salts used for chlorination include
– Lithium hypochlorite LiOCl
LiOCl + H20 Li+ + HOCl + OH-
– Sodium hypochlorite NaOCl
NaOCl + H20 Na+ + HOCl + OH-
– Calcium hypochlorite Ca(OCl)2
Ca(OCl)2 + 2H20 Ca2+ + 2HOCl + 2OH-

Combined Chlorine - Chloramination

• Chlorine (HOCl and OCl-) reacts with ammonia


to form chloramines, commonly referred to as
‘combined chlorine’
• The predominate species are monochloramine
and dichloramine. A small fraction is
trichloramine or nitrogen trichloride

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Breakpoint Curve

Cl2:N < 5:1 Cl2:N > 5:1 Cl2:N > 9:1


Total Chlorine Residual

Free Residual

Breakpoint
Dichloramine
predominates

Monochloramine
predominates

A B C
Chlorine Added

Breakpoint Curve Considerations


• Shape of the curve is dependent upon
– amount of ammonia and other chlorine demand
substances in the water
– temperature
– pH
– contact time
• Most effective disinfection, least taste and odor
occurs with free residual chlorine
• Free chlorine may lead to formation of DBP

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Chloramination

• Chloramination: Purposeful use of chlorine and


ammonia to form monochloramine.
– Minimizes formation of chlorinated organics
– Ammonia to chlorine Ratio is controlled to favor
formation of monochloramine, typically 5:1 Cl2:N
• Total residual chlorine test: All free and
combined chlorine species

Chloramine Formation
• Monochloramine - NH2Cl
NH3 + HOCl NH2Cl + H2O
• Dichloramine - NHCl2
NH2Cl + HOCl NHCl2 + H2O
• Tricholoramine (Nitrogen Trichloride) - NCl3
NHCl2 + HOCl NCl3 + H2O
• Chloramines are not as effective disinfectants as
free chlorine

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Definition of Unreacted Ammonia

• Ammonia in solution as
– NH3 Free ammonia gas dissolved in water or;
– NH4- The ammonium ion

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Breakpoint curve for chlorination and chloramination


Cl2:N <5:1 Cl2:N >5:1 Cl2:N >9:1

Total Ammonia Dichloramine


Formation

Free Ammonia
Total Residual Chlorine
Total and Free Ammonia

Monochloramine Free Residual


Formation Chlorine

Chlorine Added
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Calculate Ratio as Cl2:N!
Atoms/
Ammonia, Atomic
molecule
NH3 mass

Nitrogen 14 X 1 = 14
Hydrogen 1 X 3 = 3
Molecular
= 17
Weight (Mass)
3 x 100
Percent Hydrogen = 17.6
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If the feed rate is calculated on NH3 as NH3 instead of as N,
the feed rate is off 17.6%!
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Effect of pH on Chloramine Species


100 0

90 10
• Distribution of
80 20
chloramine
species is
% Monochloramine

70 30
% Dichloramine

60 40 effected by:
50 50

40 60
– pH
– Ammonia
30 70

20 80

10 90
concentration
(see breakpoint curve)
0 100
5 6 7 8 9

pH
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Comparison of Methods
Method Range Detection %RSD Use Skill
mg/l Level*
DPD colorimetric 0-5 0.005 1-2 F&T 1
Ultra low-range
0-0.500 0.002 5-6 T 2
DPD colorimetric
DPD titration 0-3 0.018 2-7 F&T 2
Iodometric Up to Total
1 NR 2
4% Oxidants
Amperometric
Up to 10 0.015 1-2 F&T 3
Titration - Forward
-Back 0.006-1 0.006 15 T 3
Electrode Total
0-1 0.05 10 2
Oxidants
Monochlor-F W 0-4.5 Mono-
0.09 2 1
WW 0-10 chloramine
Skill Level: 1= Minimal training; 3 = Experienced
*Under ideal laboratory conditions. Practical limit for all
methods is really about 0.02
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DPD-Chlorine Reaction Products

H H H H H H H H
N+ N+ N+

Cl2
+

N+ N+ N+
Et Et Et Et Et Et
H
AMINE WÜRSTER DYE IMINE
(colorless) (magenta colored) (colorless)

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DPD Würster Dye Absorbance Curve

530 nm
Maximum sensitivity 512 nm 553 nm
510-515 nm

0.2500
Absorbance

0.1500

0.0500

400.00 440.00 480.00 520.00 560.00 600.00


Wavelength, nanometers

Colorimetric Methods – Lab or Field Use

Chlorine – DPD
Chloramination – MonoChlor F

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Measuring Free and Total Residual

• Free residual • Total residual


measurement measurement
– Add sample to sample – Add sample to sample
cell cell
– Blank – Blank
– Add reagents – Add reagents
– Read within 1 minute – Wait 3 minutes
– Read within 3-5
minutes

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Test Kits

Compara Test
-tors Strips

Chlorine X X
MonoChloramine NA NA

Avoid use of color comparators for


regulatory reporting due to
subjective errors

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Common Interferences
• Other oxidants: ClO2, • Buffer capacity
O3, Br2, H2O2, I2, • Sample color
KMnO4 • Mn+3 to Mn+7
• Disinfection by- • Cr +7
products, I.e. chlorite
• Organic N-Cl (organic
and chlorate
chloramines in
• Particulate wastewater)
contamination -
turbidity

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Compensating for Manganese Interference


• Split sample. Analyze • Subtract result of
first portion as usual second portion from
• Second Portion: first portion
– Adjust pH w/1N
Sample
sulfuric acid Size 5 ml 10 ml 25 ml
– Add drops of 30 g/l Adjust to Adjust to Adjust to
H2SO4, 1N
potassium iodide; pH 6-7 pH 6-7 pH 6-7
wait one minute Potassium
– Add drops of 5 g/l Iodide, 2 drops 2 drops 3 drops
sodium arsenite 30 g/l
Sodium
– Add DPD and Arsenite, 2 drops 2 drops 3 drops
complete test 5 g/l

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Chemistry of Amperometric Titration
• For total chlorine determinations, KI is oxidized by chlorine and
chloramines, at pH 4, to form tri-iodide:

Cl2 + 3KI → I 3− + 3K + + 2Cl −


• Then the two half reactions are :

I 3− + 2e − → 3I −
• Stoichiometry is thus 2:2 (titrant : sample)

PhAsO + 4 H 2 O → PhAsO(OH )2 + 2 H 3O + + 2e −

Forward Titration
• Amperometry
– Electrochemical technique in which a small electrical
voltage is applied across two electrodes
– Chemical reactions caused by titrant addition cause a
change in current, which is measured and recorded
by the instrument

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Forward Titration
• Amperometry
– Results are obtained by calculating the current
change as a function of the amount of titrant added

Forward Titration
• Amperometry
– A potential is applied across the electrodes prior to
the titration.
– Buffer is added to the sample and KI is added to total
chlorine samples

Potential Applied

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Forward Titration
• Amperometry
– Current can flow as long as there is a substance that
can be reduced at the cathode (+) and oxidized at the
anode (-).

+ -

Forward Titration
• Amperometry (for free residual chlorine)
– Chlorine is titrated with PAO titrant. The chlorine is
reduced at the cathode. The PAO is oxidized at the
anode.

Chlorine reduced + - PAO Oxidized


(or iodine for total
chlorine determination)

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Forward Titration
• Amperometry
– The more chlorine (or oxidant) in solution, the greater
the amount of current flow.

Current

Forward Titration
• Amperometry
– As the PAO titrant is added, the PAO reduces the
chlorine, and the chlorine concentration decreases.

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Forward Titration
• Amperometry
– As the chlorine concentration decreases, the amount
of current also decreases.

Current

Forward Titration
• Amperometry
– When all of the chlorine has been reduced by the
PAO, the amount of current falls to near zero.

Current

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Forward Titration
• Amperometry
– The chlorine concentration is calculated based on the
amount of PAO added to reduce the measured
current to zero.

Typical Amperometric Titration System

Titrant
delivery
system
Dual Platinum
or
Silver/Platinum
Electrode Microampere
1.123
meter

Magnetic
Stirrer

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Forward Titration

• Titration curves and calculations

On-line Chlorine Measurement

Amperometric
Probe – Free or
Total Chlorine

Monochlor F –
Monochloramine,
Colorimetric
Free and Total
DPD – Free or
Ammonia
Total Chlorine

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Online Chlorine Monitoring –
Major Technologies

Colorimetric: Amperometric:
measuring intensity of color developed measuring electrical current
by reaction of chlorine with indicator generated in a circuitry by reaction of
(chemical compound, e.g. DPD). The chlorine with electrodes . The larger
deeper color, the higher chlorine current value, the higher chlorine
concentration. concentration.
Main Differentiators: Main Differentiators:
• Independent of major sample • No chemical reagents required
parameters (pH, flow, temperature),
• Fast response to analyte
• Established calibration curve concentration changes

Really?

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Online Chlorine Monitoring Comparison

Colorimetric Amperometric
Pros Pros
•Accuracy - no calibration •Fast response
•Unattended operation •Reagentless technology
(up to 30 days)
•No waste stream?
•Predictable and simple
maintenance
•Results independent of
changes in sample pH, Really?
temperature, conductivity,
sample pressure
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Online Chlorine Monitoring Comparison

Colorimetric Amperometric
Cons Cons
•Reagents and waste •Greater influence from
stream management sample pH, temperature,
flow, pressure, Cl2
concentration, etc.

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Keys to Application Success


Steps to choosing your chlorine analyzer:
1. Look at the instrument's major performance
specifications to make your initial decision.
• Chlorine concentration range
• Sample pH range
2. Next, consider each technology's key differentiators to
determine which is preferred for your application.
• Colorimetric
• Amperometric
3. Finally, consider the treatment process details - key to
application success to make sure that your preferred
instrument is right for your application.

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CL17 Chlorine Analyzer Pocket Colorimeter

Use a portable colorimeter


to verify operation of on-
line chlorine analyzers. Do
not use color comparitors
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Monitoring Hypochlorite and Aqua


Ammonia Bulk Solutions

• Know what you’re buying


• Know the concentration
being used
• Digital Titration or drop
count (Bleach only)
• 5-15%

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Contact Information
N Illinois S Illinois
Paul Gauger Brad Baldwin
Hach Company Hach Company
800-227-4224 X2060 800-227-4224 X2327
pgauger@hach.com bbaldwin@hach.com

Terry Engelhardt
Hach Company
Application Development Manager –
Drinking Water
800-227-4224 X2327
tengelha@hach.com

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